Palladium Reagents and Catalysts Innovations in Organic Synthesis

by Tsuji, Jiro

• ISBN13: 9780471972020
• ISBN10: 0471972029
• Edition: 1st
• Format: Paperback
• Copyright: 1997-03-04
• Publisher: Wiley

Summary

Palladium Reagents and Catalysts Innovations in Organic Synthesis Jiro Tsuji Okayama University of Science, Okayama, Japan Palladium Reagents and Catalysts brings to synthetic organic chemists the many applications of organopalladium chemistry, highlighting the most recent discoveries in this rapidly expanding field. This volume provides a comprehensive overview of the development of many innovative synthetic methods, using palladium reagents either as catalysts or stoichiometric reagents. Palladium is the most versatile of the transition metals used in organic synthesis and knowledge of this rapidly expanding and challenging area is essential for all synthetic organic chemists. Palladium Reagents and Catalysts fulfils, systematically and efficiently, the urgent need for understanding the essence of organopalladium chemistry. Palladium Reagents and Catalysts presents: * a complete coverage of nearly 35 years of organopalladium chemistry * an in-depth treatment of many innovative synthetic methodologies * rational classification of all reactions according to reaction mechanism * a concise survey of the scope and limitations of organopalladium reagents * extensive references to the primary literature Providing comprehensive coverage of all important reactions of organopalladium reagents, Palladium Reagents and Catalysts demonstrates applications to organic synthesis, recommending possible future research. Industrial and research chemists working on synthetic methodologies and organometallic reactions as well as organic, natural product, pharmaceutical, organometallic and fine chemical synthesis, will find Palladium Reagents and Catalysts an essential reference source and indispensable research companion.

Author Biography

Jiro Tsuji, Okayama University of Science, Okayama, Japan, is the author of Palladium Reagents and Catalysts: Innovations in Organic Synthesis, published by Wiley.

Table of Contents

Preface	xi	(2)
Abbreviations	xiii
1 The Basic Chemistry of Organopalladium Compounds	1	(12)
1 Characteristic Features of Pd-Promoted or -Catalyzed Reactions	1	(1)
2 Palladium Compounds, Complexes, and Ligands Widely Used in Organic Synthesis	1	(4)
3 Fundamental Reactions of Pd Compounds	5	(5)
3.1 `Oxidative' Addition Reaction	5	(1)
3.2 Insertion Reaction	6	(2)
3.3 Transmetallation Reaction	8	(1)
3.4 The Final Step of Pd-Promoted or -Catalyzed Reactions	8	(1)
3.4.1 Reductive Elimination Reaction	8	(1)
3.4.2 Elimination of B-Hydrogen	9	(1)
3.5 How are Catalytic Reactions Possible?	9	(1)
4 References	10	(3)
2 Classification of the Reactions Involving Pd(II) Compounds and Pd(0) Complexes in This Book	13	(6)
1 Stoichiometric and Catalytic Reactions	13	(1)
2 Stoichiometric Oxidative Reactions with Pd(II) Compounds in which Pd(II) is Reduced to Pd(0)	13	(2)
3 Catalytic Reactions Mainly with Pd(0) Complexes	15	(1)
4 The Characteristic Features of Pd--C Bonds	16	(2)
5 References	18	(1)
3 Oxidative Reactions with Pd(II) Compounds	19	(106)
1 Introduction	19	(2)
2 Reactions of Alkenes	21	(40)
2.1 Introduction	21	(1)
2.2 Reaction with Water	22	(9)
2.3 Reactions with Alcohols, Phenols, and Other Hydroxy Compounds	31	(6)
2.4 Reactions with Carboxylic Acids	37	(5)
2.5 Reactions with Amines	42	(5)
2.6 Reactions with Carbon Nucleophiles	47	(3)
2.7 Oxidative Carbonylation	50	(5)
2.8 Reactions with Aromatic Compounds	55	(4)
2.9 Reactions with Hydrogen Cyanide and Chloride	59	(1)
2.10 Oxidative Coupling Reactions	59	(1)
2.11 Reactions with Alkynes	60	(1)
3 Stoichiometric Reactions of -Allyl Complexes	61	(5)
3.1 Stoichiometric and Catalytic -Allylpalladium Chemistry	61	(1)
3.2 Preparation of -Allylpalladium Complexes from Alkenes and Their Reactions with Carbon Nucleophiles	62	(2)
3.3 Carbonylation, Elimination, and Oxidation Reactions	64	(2)
4 Reactions of Conjugated Dienes	66	(8)
5 Reactions of Aromatic Compounds	74	(5)
5.1 Homocoupling Reactions	74	(2)
5.2 Oxidative Substitution Reactions	76	(3)
6 Synthetic Reactions by Transmetallation of Organometallic Compounds	79	(8)
7 Synthetic Reactions Based on the Chelation of Heteroatoms	87	(10)
7.1 ortho-Palladation of Aromatic Compounds	87	(8)
7.2 Reactions of Allylic and Homoallylic Amines and Sulfides	95	(2)
8 Reactions of Alkynes	97	(5)
9 Reactions of Allenes	102	(2)
10 Enone Formation from Ketones, and Oxidation of Alcohols	104	(1)
11 Oxidative Carbonylation Reactions	105	(3)
12 References	108	(17)
4 Catalytic Reactions with Pd(O) and Pd(II)	125	(403)
1 Reactions of Organic Halides and Pseudo-Halides Catalyzed by Pd(0)	125	(165)
1.1 Aryl, Alkenyl, Benzyl, and Alkynyl Halides, and Their Pseudo-Halides	127	(126)
1.1.1 Reactions with Alkenes, and 1,2-, 1,3-, and 1,4-Dienes	127	(41)
1.1.1.1 Intermolecular reactions with alkenes	127	(22)
1.1.1.2 Intramolecular reactions with alkenes	149	(14)
1.1.1.3 Reactions with 1,2-, 1,3-, and 1,4-dienes	163	(5)
1.1.2 Reactions with Alkynes	168	(20)
1.1.2.1 Terminal alkynes to form alkenyl- and arylalkynes	168	(10)
1.1.2.2 Internal alkynes (including reactions with terminal alkynes by insertion mechanism)	178	(10)
1.1.3 Carbonylation	188	(21)
1.1.3.1 Formation of carboxylic acids and their derivatives	188	(11)
1.1.3.2 Formation of aldehydes	199	(1)
1.1.3.3 Formation of ketones	200	(9)
1.1.4. Reactions with Organometallic Compounds of Main Group Metals via Transmetallation	209	(35)
1.1.4.1 Organolithium and -magnesium compounds	209	(3)
1.1.4.2 Organozinc compounds	212	(6)
1.1.4.3 Organoboron compounds	218	(9)
1.1.4.4 Organoaluminum and -zirconium compounds	227	(1)
1.1.4.5 Organotin compounds	228	(11)
1.1.4.6 Organosilicon compounds	239	(3)
1.1.4.7 Organocopper compounds	242	(1)
1.1.4.8 Organophosphorus compounds	243	(1)
1.1.5 Displacement Reactions with Carbon, Oxygen, and Sulfer Nucleophiles	244	(4)
1.1.6 Hydrogenolysis with Various Hydrides	248	(2)
1.1.7 Homocoupling (Reductive Coupling) of Organic Halides	250	(1)
1.1.8 Reactions of Aromatic Compounds	251	(2)
1.2 Acyl and Sulfonyl Chlorides and Related Compounds	253	(8)
1.3 Alkyl Halides, Polyhalides, -Halo Ketones and Esters	261	(4)
1.4 References	265	(25)
2 Reactions of Allylic Compounds via -Allylpalladium Complexes Catalyzed by Pd(0)	290	(132)
2.1 Reaction Patterns and Various Allylic Compounds Used for Catalytic Reactions	290	(2)
2.2 Allylation Reactions	292	(48)
2.2.1 Stereochemistry	292	(5)
2.2.2 Allylation of Soft Carbon Nucleophiles	297	(1)
2.2.2.1 Allylation under basic conditions	298	(21)
2.2.2.2 Allylation under neutral conditions	319	(10)
2.2.3 Allylation of Other Nucleophiles	329	(11)
2.3 Carbonylation	340	(5)
2.4 Reactions of Hard Carbon Nucleophiles via Transmetallation	345	(11)
2.4.1 Cross-Coupling of Allylic Groups with Hard Carbon Nucleophiles	345	(8)
2.4.2 Formation of Allylic Metal Compounds	353	(3)
2.5 1,4-Elimination to Form Conjugated Dienes	356	(7)
2.6 Preparation of B-Unsaturated Carbonyl Compounds by the Reactions of Silyl Enol Ethers and Enol Acetates with Allyl Carbonates	363	(1)
2.7 Oxidation of Alcohols via Allyl Carbonates	364	(2)
2.8 Hydrogenolysis of Allylic Compounds	366	(3)
2.9 Allyl Group as a Protecting Group	379	(6)
2.10 Reactions of Allyl -Keto Carboxylates and Related Compounds	385	(10)
2.10.1 Decarboxylation and Allylation	385	(3)
2.10.2 Decarboxylation and Elimination (Enone Synthesis)	388	(3)
2.10.3 Decarboxylation and Deacetoxylation (Preparation of -Methylene Compounds)	391	(1)
2.10.4 Aldol Condensation and Michael Addition	392	(1)
2.10.5 Decarboxylation and Hydrogenolysis	393	(2)
2.11 Reactions of Alkenes and Alkynes	395	(4)
2.12 Allylic Rearrangement, Claisen Rearrangement, and Related Reactions Catalyzed by Pd(0) and Pd(II)	399	(5)
2.13 Reactions of 2,3-Alkadienyl Derivatives	404	(2)
2.14 References	406	(16)
3 Reactions of Conjugated Dienes Catalyzed by Pd(0)	422	(28)
3.1 Dimerization and Telomerization of Conjugated Dienes and Related Reactions	423	(18)
3.1.1 General Reaction Patterns	423	(1)
3.1.2 Dimerization and Related Reactions	424	(3)
3.1.3 With Water, Alcohols, and Phenols	427	(2)
3.1.4 With Carboxylic Acids	429	(1)
3.1.5 With Ammonia and Amines	430	(2)
3.1.6 With Enamines and Carbon Nucleophiles	432	(2)
3.1.7 With B, Si, and Sn Compounds	434	(3)
3.1.8 Carbonylation	437	(1)
3.1.9 Co-cyclization with Aldhydes, Isocyanates, and Imines	438	(1)
3.1.10 With Carbon Dioxide	439	(1)
3.1.11 With SO2, CS2, and S	440	(1)
3.1.12 With Other Nucleophiles	440	(1)
3.2 Miscellaneous Reactions	441	(1)
3.3 Synthetic Applications of Butadiene Telomers	441	(5)
3.4 References	446	(4)
4 Reactions of Allenes Catalyzed by Pd(0)	450	(3)
4.1 References	452	(1)
5 Reactions of Propargylic Compounds Catalyzed by Pd(0)	453	(18)
5.1 Reaction Patterns	453	(2)
5.2 Reactions with Alkenes and Terminal Alkynes	455	(1)
5.3 Carbonylation	456	(6)
5.4 Hydrogenolysis	462	(2)
5.5 Reactions with Carbon and Oxygen Nucleophiles, and Other Reactions	464	(4)
5.6 Preparation of Enynes by Elimination	468	(1)
5.7 Miscellaneous Reactions Catalyzed by Pd(0) and Pd(II)	469	(1)
5.8 References	470	(1)
6 Reactions of Alkynes Catalyzed by Pd(0) and Pd(II)	471	(39)
6.1 Carbonylation	471	(4)
6.2 Coupling Reactions	475	(1)
6.3 Cyclization of Nonconjugated Enynes, Diynes, and Triynes	476	(12)
6.4 1,2-Dimetallation, Hydrometallation, and Hydrogenation Reactions	488	(9)
6.5 Addition of Carbon, Oxygen, Nitrogen, and Sulfur Nucleophiles	497	(6)
6.6 Isomerization	503	(1)
6.7 Miscellaneous Reactions	504	(2)
6.8 References	506	(4)
7 Reactions of Alkenes Catalyzed by Pd(0) and Pd(II)	510	(18)
7.1 Carbonylation	510	(6)
7.2 Addition Ractions (Oligomerization and Co-oligomerization)	516	(1)
7.3 Hydrosilylation, Bis-silylation, and Reduction	517	(4)
7.4 Reactions of Methylenecyclopropanes	521	(2)
7.5 Miscellaneous Reactions	523	(2)
7.6 References	525	(3)
5 Various Reactions Catalyzed by Pd(II) and Pd(0)	528	(22)
1 Exchange Reactions of Alkenyl Ethers and Esters Catalyzed by Pd(II)	528	(3)
2 Palladium-Catalyzed Decomposition of Azo Compounds, Azides, and Peroxides	531	(2)
3 Cope Rearrangement and Related Reactions	533	(4)
4 Decarbonylation of Aldehydes and Related Compounds	537	(1)
5 Reactions of Carbon Monoxide and Carbon Dioxide	538	(3)
6 Reduction	541	(1)
7 Miscellaneous Reactions	542	(3)
8 References	545	(5)
Index	550